DE1568890A1 - p-Ethylbenzaldehyde derivatives and process for their preparation - Google Patents

Description

DR. BERG DIPL.-ING. STAPF

PATENT Attorneys 1 568830

8 MUNICH 2, H ILBLESTR ASS E 2O

Dr. Berg Dipl.-Ing. Stopf, 8 Munich 2, Hllblestrgfle 20

Our sign l4 546 Date 23.10

File number: P 15 68 890.1-42
New documents

Lawyer file no. 14 546

Instytut Badan Jadrowyeh, Warszawa / Poland Inventor: Doz.Dr. Andrzej feukasiewicz

"p-Ethylbenzaldehyde Derivatives and Processes for Their

Manufacture "

The invention relates to p-ethylbenzaldehyde derivatives and processes for the preparation of these compounds of the general

bad orf) cfif? A? 16/1768

my formula I.

OCH- (y /) - CH-CX, (I)

HNR

in which X is chlorine or bromine and R is alkyl with 3 to 6 carbon atoms, benzyl, α-phenylethyl, 0-phenylethyl, cyclopentyl, cyclohexyl or 2-tetrahydropyranmethyl.

The process according to the present invention for the preparation of compounds of the formula I is based on the fact that one compounds of the general formula II

I = NR (II)

R ¹ N = CH-Yv / V ⁰¹¹

in which R has the above meaning and R is the same as R or an aromatic radical, with a trihaloacetic acid of the general formula

CX ₃ COOH

wherein X has the same meaning as above, is reacted in an organic solvent and the product obtained is hydrolyzed.

BAD ORIGINAL 3 -009816/1768

The reaction is advantageously carried out by dropwise addition of a solution of the trihalogenosylgic acid in toluene or benzene in an equimolar amount of the imine, also in toluene or benzene solution at a temperature of 70 to 90 ° C.

After the post-reaction mixture has been previously shaken with dilute hydrochloric acid, the reaction product is separated off as the hydrochloride for hydrolysis of the azomethine group, for example by saturating the solution with hydrogen chloride after the reaction has ended. The final product is obtained in pure form by shaking the Hydrochloride with a two-phase mixture of water, organic solvent. Thanks to the weak basicity of the p- (a-AminO'ßjß, ß-trihaloethyl) benzaldehyde derivatives, the hydrochloride is subject to hydrolysis and the free compound is transferred quantitatively into the organic layer. If a greater than equimolar amount of trihaloacetic acid is used for the reaction with imines in which R = R, the corresponding diamine of the formula P-CgH ₁ - (CH.CCl, .NHR) ₂ is also formed at the same time. The use of mixed imines, in which R is an aromatic radical, permits the easy recovery of aromatic amine (e.g. aniline) which, due to its poor solubility in water, is formed as a result of hydrolysis of the reaction product. This goes out

009816/1768

from the following reaction scheme:

CX COOH ₁

1 >. R ¹ N = CH- (V /> -CH-CX, + CO »t

I ^{3 2}

HNR

I + R ¹ NH ₂ -HCl

However, the yields of the reaction are usually lower than with symmetrical mines in which R = R.

The applied in the process according to the invention p-xylylidenimine is by heating 1 mole of terephthalaldehyde with 2 mol of a primary amine of the formula RNH- obtained, in which R has the meaning given above.

The reaction is carried out in benzene or toluene, with the water of reaction is removed as an azeotrope.

The imine solution obtained in this way can be used without prior isolation of the product can be used for the reaction with trihaloacetic acid.

Mixed imines (R = aryl) are obtained by heating the

009816/1 768

Terephthalaldehyde initially with the aromatic amine and then with the aliphatic amine, e.g., in ethyl alcohol, preferably in approximately molar proportions. After removing the solvent, the residue is dissolved in toluene or benzene and the procedure is then continued as in symmetrical imines (R = R).

The N-substituted p- (α-amino-ß, ß, ß-trihaloethyl) -benzaldehyde derivatives prepared by the process according to the invention show an anti-tumor as well as a fungicidal effect, as well as an effect against viruses. she can also serve as intermediates for further syntheses of biologically active compounds.

(a-Trihalomethyl) amines, which contain an aromatic radical contain bound to the carbon atom of the group X-C-CH-NH, represent bases of selective affinity (acceptor) towards anions and inert substances with electron donating properties and can therefore be used for the Production of selective anion exchange adsorbers can be used. As starting compounds for this Derivatives according to the invention are used, which with regard to the presence of reactive aldehyde groups can be chemically linked with adequate polymers.

BATH ORIGINAL

009816 / 176B

mute

JLJL-JL.

ρ * (ui ^ n-

(5, * g) Was heated to boiling with ft-StttylaA & ii (6.0 g ) in toluene solution and the water was distilled as an azeotrope. After the water

in.
was removed, the imine solution thus obtained was slowly added dropwise to a solution of 6.8 g of trichloroacetic acid in toluene at a bath temperature of 90 to 95 ° C. The reaction mixture was then heated until the evolution of carbon dioxide had ended (about 1 hour).

After cooling to room temperature, the mixture was shaken with 0.5N HCl and most of the toluene was removed from the solvent layer. To the residue a small amount of ethyl acetate was added and then saturated with hydrogen chloride. The precipitated hydrochloride precipitate was filtered off, washed on the filter with ethyl acetate and dried in a vacuum desiccator. The amount of crude product was 13 * 7 g. The hydrochloride was decomposed by shaking with a mixture of benzene / water, part of the solvent was removed from the benzene layer and then amine hydrochloride was precipitated again in the same manner as described above. The purified product

009816/1788

The product decomposes at over 20O ⁰ C.

Analysis for C ₁₃ H ₁₇₁₁

Found: C 44.85 * ^H *> 9% N 4.35 * Calculated: C 45.2 * H 4.955 N 4.05 *.

Example 2 p- (α-Cyclopentylamine-ß, ß, ß-trichloroethyl) benzaldehyde.

Terephthalaldehyde (5.4 g) was made as above with 7.0 g of cyclopentylamine heated and to the imine solution obtained at a bath temperature of 90 to 95 ° C 6.8 g dissolved in toluene Trxchloroacetic acid was added dropwise. After treatment as in Example 1, 13.0 g of crude hydrochloride were obtained decomposed after cleaning as above at over 200 C.

Analysis for C ₁₁₁ H ₁₇₁₁

Found: C 46.4 * H 4.75 * N 4.356 Calculated: C, 47.05 * H 4.75? N 3.9 *

The product may still contain a small amount of diamine hydrochloride (PC ₆ H ₁₁ (CHNHC ₅ H ₁₀ ) .2HCl),

CCl ₃

which you can, for example, by recrystallization of the free Can remove amines from alcohol or gasoline.

- 8 009816/1768

ρ- (α-Cyciopentylarain-β, β, β-trichloroethyl) benzaldehyde is a crystalline body having a melting point of 10J »to 105 ⁰ C. The diamine content is increased with use of higher than equimolar amount Trichloreseigsäure.

- 9. -009816/1768

Claims (2)

Claims 1. Compounds of the general formula I OCH - <\ /> - CHr-CX ₃ (I) HNR in which X is chlorine or bromine and R is alkyl with up to 6 carbon atoms, benzyl, α-phenylethyl, 0-phenylethyl, Is cyclopentyl, cyclohexyl or 2-tetrahydropyranmethyl. 2. Process for the preparation of compounds of the general formula I given in claim 1, characterized characterized in that compounds of the general formula II R ¹ N = CH-Vv /> - CH = NR (II) in which R has the meaning given in claim 1 and R is R or an aromatic radical, with a trihaloacetic acid of the formula CX ₃ COOH wherein X is chlorine or bromine, reacted in an organic solvent and hydrolyzed the product obtained. 009816/1768 New documents (au. 7 s 1 aim. 2 Mr. 1 sntz 3 a ^ inderunaee · «. V. 4.».